Process of making varnish material.



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To all whom it may concern U Be it known that I, OARnn'roN Ennis, a citizcn-of .the United States, and 'a resident of Montclair, in the county of Essex and State of New Jersey, have invented certainnew and useful Improvements in Processes of Making VarnishMaterial, of which the following is a specification. This invention relates to a method of making varnish resin materials and the l ke including resin esters and to the roduct of such process and relates in particular to a method which involves certain improved or simplified operations and enables esters, anhydrids, lactones and the like, in some cases of almost complete neutrality to be prepared. k

Rosin and other similar resins contain a large amount of acid material which colopho nium very readily unites with basic bodies, such as white lead and zinc white, and when rosin, for. example, is used as a component of grinding or mixing varnish the pigment combines withthe resin acid and livering results, causing thickening of the product. To ameliorate this diiiiculty to some extent,

. rosin has been hardened by lime or other alkali which only partly neutralizes the acid. Lime resinate of a more neutral char; acter would be too slightly soluble in the vehicle employed. Lime treatment therefore, does not overcome the difiiculty. By esterifying resin with glycerin or other bodies containing the hy roxyl group, mcluding the alcohols, sugars and also .even that other class of hydroxylated bodies, the phenols, esters can be obtained which do not react deleteriously with the basic pigment employed. As ordinarily pre ared, however, theseproducts have the isadvantage of containing a certain amount of free acid,

as for exam lo, a commercial 'sam le of rosin ester w ich was found to exhi it an acid number of about 50. Furthermore, the present method of making ester, or fester" gum as it is known to the trade, involves f heating the material under a pressure of sevoral atmospheres, and then distilling in cacao, which involvesa seriesof operations with a plant of a costly character.

By the present invention it is possible to entirely ehminatethe' operation under pres- 'j specl fleatlon ofletteralatent. Patented @Cti. 9,1917. Application matriar h m, ma: 4 Serial No. mesa.

' sure and in cacao, although these may 3e usedwith the presentprocess, if 'any vantage under special circumstances is de rived by so doing. According to one illustrative form of the present invention ordinary rosin is treated with -gl cerin at an elevated temperature and un er approximately atmospheric pressure with vigorous agitation while employing an excess of glycerin which is in part com-bined with the rosin and 'in part vaporized. The vaporized portion mingled with any water that may have formed duringreaction is passed through a vertical separator and the con- 'nrneaansianv densed glycerin is returned to the container in-which the reaction is taking place while more or less of the steam, arising from the water produced by the reaction or from materials which are not of an-anhydrous character, pass away. Rosin spirits or other volatile organic material of similar charac the steam. Thus the volatilized glycerin is being constantly returned to the reaction chamber and'an excess maybe maintained so that reaction with the rosin takes places ter may also be removed in part along with i more readily than is the case when a merely suflicient quantity of glycerin is added to bring about the reaction. When rosin withan equivalent quantity of glycerin is hcated the combination of the glycerin. with the rosin diminishes the amount of glycerin while'some of the latter is lost by distillation, etcx, so that toward the end of the reaction only a small amount ofiglycerin may be present, while the conditions of esterification have reached the maximum of slowness. The presence'of anexcess of glycerin at this stage enables the reaction to take place to a desired degree without loss of costly material. I

When rosin is heated in the neighborhood of 300 (3., for some time it loses a considerable amount of water forming anhydrids like material. a If the rosin is heated in the presence of an adjacent mass of lime so that water is absorbed the reaction goes to substantial com letion forming anhydrid-like material. Titration with alcoholic potash apparently gives the total acidity as free acid and anhydrid, while titration with I alfueous solutions gives the acidity in terms lid ' sure and catalytic material.

of free acid only. When the above product is heated with glycerin reaction takesplace giving a species of ester lactone product.

Tn heating rosin and glycerin when conditions are such that water isbeing evaporated, especially the water Originally present as molsture in the glycerin, considerable foaming occurs to 200 or thereabout and the contents of the reaction vessel are liable to boil over. To obviate this a smallamount of rosin with the glycerin is heated with agitation until a good part of the water'is expelled and the remainder of the rosin then added, when the entire mixture is esterified.

Besides rosin, other resins such as the copal gums and the like may be esteritied as also mixtures of these. gums with rosin. Benguela, Angola, Java, anila, kauri and other copals, shellac, dammar, sandarac, and so-called South American or Brazilian copal and the like are included. Kongo copal gum is used herein in an illustratlve manner. Resin obtained by extracting chips or dust of these materials, with suitable solvent-s may be used.

The sugars and starches are cheap sources of esterifying agents but carbohydrates such as glucose and related sugars have a tendency to darken during the heating, possibly by the formation of caramel. it is therefore desirable to carry on the reaction in this case at the lowest possible temperature vhich may-be done by the passage of an inert gas through the mass particularly in conjunction with reduced atmospheric pres- The mixture is placed in a heated agitator and an inert fitted with an agitator.

gas is passed through the mass while the latter is violently agitated." A vacuum pump communicating with the top of the closed reaction chamber enables the vola- Qtilized products of reaction to be removed and glycerin, if usedwith the sugar may be duly returned.

If the product is found to be not sufiiciently hard for some varnish compositions it may be treated with a current of steam, preferably superheated, which removes the volatile constituents causing the material to vwith agitation-or bypassage of inert gas through the mass at the requisite temperature.

As an example 100 lbs. of rosin are heated with 12 lbs. of glycerin in a closed vessel I A vertical separator attached to the top of the vessel enables a return of the volatilized glycerin. The temperature is maintained for one to three hours at 260-to 290 0., then the vertical meager separator is cut ed and the material heated with agitation for an hour or more at approximately the same temperature until volatile rosin spirits and excess of glycerin have been removed. The product is preferably cooled out of contact with the air then removed by steam or vacuum distillation.

The reaction between divers resins or resinous materials and esterifying materials is facilitated by the use of catalyzers, and agents such as aluminum oxid and titanium oxid may be used to efi'ect an acceleration of, or otherwise improve the reaction or better the completion thereof. In place of aluminum oxid a few per cent. of aluminum salts such as aluminum acetate may be added to the material or finely dividedaluminum or the metal in the form of scales. Satisfactory results may be obtained by using rcceptacles of aluminum, in which vessels the reaction takesplace without discoloration of the product. The present invention therefore embraces the formation of ester material in contact with aluminum material and the like.

In the treatment of copal gums and similar hard resins some modification is ordinarily desired of the foregoing and the following will thereof: V

A quantity of Kongo copal resin or gum was heated in a closed receptacle provided with a condenser, the heating being carried on for about three and a half hours at approximately 315325 C. About 12-15% of oily distillate was collected. At the end of this operation the resin was found to be completely soluble in benzol and the acid number was found to be 88 when titrated with alcoholic potash. One sixteenth part by weight of glycerin was then added to the fusion. at C. In place of the ordinary condenser a reflux condenser was employed and the mixture was gradually raised .to 280 (1., under constant stirring and in contact with aluminum. After a very short time the mass was-converted into a spongy product, which solidified to a firm mass on cooling. It was not readily soluble in benzol and was very hard and somewhat darker in color than the original Kongo resin. This material was heated to slightly above 360 (3., for a time when the acid number was found to be about 20. By operillustrate one modification.

atmospheric pressure using the se arator aforesaid the'water is removed whi e glycerin is constantly returning to the superheated mass. If the esterification is carried out at temperatures well above 300 0., 1n

the case of the copals, -the water is rapidly eliminatedand the ester formed while keepin%the mass in a liquid state.

y the method of heating with avertica'l separator rosin esters having an-acid number below 10 and often only 5 or 6 may be obtained. They may be used in varnishes without further hardening; Such products form a part of the present invention.

A varnish ester or other resin or composite resin esters or rosin anhydrid or similar productof the process herein set forth may be melted and incorporated with varnish oils such as boiled oroxidized lin-' seed or Chinese wood oil, or perilla oil and in some cases fish or whale. oils and the semi-dryin oils, such as cottonseed, corn, rape and t 0 like. When the drying features of the oils are not taken into consideration, mineral oil may be introduced more or less. The composition is made up with varying proportlons of the oil and resinous material, using a larger proportion to make the lon oil varnishes and smaller propor. tions 0 oil in the case of short oil varnishes. When prepared for use as a varnish where the acidity of the composition is not a factor, various acid resins or otherwise, may be incorporated with the composition. When used for grinding or mixing varnishes, the composition should be sufliciently neutral to avoid any undesirable li-vering and may be ground with the pigments, such as zinc oxid, white lead and the like to give a paste or composition of the consistency desired.

Suitable driers and also thinners such as turpentine, benzi'n, benzol, toluol and the like may be introduced in the desired amount. A. composition prepared from rosin-Kongo copal ester may be heated finally with a small amount of lime so as to contain some lime resinate, or if desired zinc 'resinate is incorporated with about an equal amount ofChinese wood oil and linseed oil and which has been boiled to the desired varnis making consistency and is suitably thinne with benzin, or turpentine substitute and ground with a mixture of white lead and zincoxid and containing also some barytes or other suitable extending material to make a thick paste on the one hand or a liquid of the consistency of paint as may be desired.

Varnish products for enameling the interior of tin 'cansused for preserving fruits and vegetables may be prepared from. Kongo copal ester .and the like. After packaging, the tins are sterilized at a high temperature which softens many varnishes and imparts a taste to the food product. By the present method very hard products adapted to be used in enamel mixtures may beobtained.

In a similar manner Manila copal, kauri,

acid Pontianak and like resins, etc. ma be esterified. In many cases it is desirab e to use ordinary rosin in admixture therewith as it has a desirable fluxing action and the resin may be added before or after the crackingoperatlon and prior to esterilica:

tion or during the esterification operation and of course due allowance must be made for the acidity of the rosin when endeavoring to roduce a product of low acid number. ixtures of the copals and other resins. may be similarly treated. Thus mixed esters may be obtained such as the-mixed ester of, Kongo copal gum and ordinary rosin. A

. composition containing approximately equal parts of Kon o copal ester and rosin ester makes a suita le varnish for medium grade products. For higher grade products the proportion of Kongo copal gum may be increased, employing two or three parts of the latter to one part of rosin or therea'oout. In chea-per varnishes these proportions may be reversed or otherwise varied.

Kongo copal gum as esterilied above has a very high melting point and is extremely hard and more nearly resemblesamber and Zanzibar. or other rare copal resins. The present method affords a product which may, be regarded to a considerable degree as simulating natural amber in respect to hardness, etc. I

What I claim is:

1. The process of making a varnish material which comprises forming the sub drid of rosin in the presence of Kongo c'o al gum and heating such mixture wlth g yoerin; whereby the esters of glycerin are obtained.

2. The process of making a position which comprises esterifying r in-1 and copal by heating with glycerin at su stantially atmospheric pressure and at a temperature above the boiling %oint of g1 cerin.

3. The process of esteri ing copa game which comprises cracking t e 1 a to render it soluble 1n oil, in esterifying the crack '34c0 (3., and heating the num and in heating the prooluct to render it reay and permanently soluble in varnish thinners. 1

7. The process of esterifying copal gum which comprises cracking the gum to render it soluble in oil, in esterifying the crackecl heating the product to render it soluble in varnish'thinners. p

10. The processof esterifying copal s which comprises cracking the to render it soluble in oil, in esteritying the cracked. product with glycerin at a temperature above 320 (1., and in recracking the esterified material.

'11. The process of making a varnish ester which comprises esterifying together a mixture of glycerin, Kongo copal and ordinary rosin without pressure antl at a temperature above the boiling point of glycerin.

12. The process of making resin esters which comprises esterifying glycerin and hard and soft resins in the presence of 13. The process of making resin esters which comprises ritying copal It: 1 at :Hl proiuct until it becomes soluble in oil.

i aeaaei 14;, The uv-ans H resin or? which comprises esteritying hard resin material with glycerin at in the presence ofaluminum and in heating the product to render it soluble in varnish thinners.

15. The process of esteriiying copal gums which comprises cracking the gum to render 17. The process of making resin esters which comprises esterifying' hard resin material with glycerin in the presence of aluminum and in heating the product to render it soluble in varnish thinners.

18. The process of making rosin esters adapted for surface finish compositions which comprises esterifying acid resin by heating the reaction mass out of contact with discoloring agents and in contact with aluminum.

19. The process of making resin esters adapted for surface finish compositions which comprises esterifying resinous material containing rosin by heating the reaction mass in a chamber having essentially aluminum walls in contact with said reaction mass.

Signed at Montclair in the coun% of Essex and State of New Jersey this 26t day of March 1915.

- CLETON ELLIS. Wimesses:

W. 0. Hanna, B. M. Emma. 

